Trisazo compounds containing a diphenylheterocyclic component

ABSTRACT

A polyazo dye represented by the formula   WHEREIN X and Y are the same as defined above; and a method for dyeing a fibrous material using the above polyazo dye.   WHEREIN A is an aromatic ring having or not having a substituent, B is an aromatic ring having at least one substituent selected from the group consisting of amino, substituted amino and hydroxyl group; X is CH or N; Y is one species selected from the group consisting of NH, N-NH2, N-R3, O and S, R3 being a hydrogen atom, alkyl group, aryl group, amino group or omega -hydroxyalkyl group; Z is a hydrogen atom, alkali metal, -NH4 group or amine salt residue, n is 1 or 2; each of R1 and R2 is a hydroxyl or amino group, R1 being an amino group when R2 is hydroxyl group, or a hydroxyl group when R2 is an amino group; a method for preparing the above dye using an aromatic diamine having the formula of

United States Patent 1191 Konishi et al.

22 Filed: Sept. 21, 1973 21 Appl. No.2 399,555

[30] Foreign Application Priority Data Sept. 22, 1972 Japan 47-95707 52 us. or 260/152; 260/141; 260/157; 260/158 51] I111. c1. ..C09B 35/36;C09B 35/46; 1 D06P 1/18;DO6P 1/39 58 Field of Search 260/152, 157, 15s

[56] References Cited UNITED STATES PATENTS 6/1958 Mueller et al. 260/157 9/19 58' Long et al 260/152 Primary Examiner-Floyd D. Higel Assistant ExaminerC. F. Warren ABSTRACT A p'olyazo dye represented by the formula wherein A is an aromatic ring having or not having a substituent, B is an aromatic ring having at least one substituent selected from the group consisting of amino, substituted amino and hydroxyl group; X is CH or N; Y is one species selected from the group consisting of NH, NNH N-R, O and S, R being a hydrogen atom, alkyl group, aryl group, amino group or w-hydroxyalkyl group; Z is a hydrogen atom, alkali metal, -NH group or amine salt residue, n is l or 2; each of R and R is a hydroxyl or amino group, R being an amino group when R is hydroxyl group, or a hydroxyl group when R is an amino group; a method for preparing the above dye using an aromatic diamine having the formula of wherein X and Y are the same as defined above; and a method for dyeing a fibrous material using the above polyazo dye.

13 Claims, No Drawings TRISAZO COMPOUNDS CONTAINING A DIPHENYLHETEROCYCLIC COMPONENT This invention relates to novel polyazo dyes and processes for producing the same, more particularly to dyes capable of dyeing fibrous materials made of cotton, silk, wool and like fibers having hydroxyl and/or amide groups and processes for preparing the same.

Generally, polyazo dyes basically prepared from benzidine or its derivatives are well-known as dyes for fibrous materials made of fibers having hydroxyl and/or amide groups. These dyes are excellent in color, dyeability, solubility in water and chemical stability. Moreover, they assure excellent dischargeability on silk or the like. Because of these advantages, the polyazo dyes have long been used in a wide variety of applications. However, recent researches have revealed that benzidine and the derivatives thereof affect the living body medically. In fact these compounds are found to be very likely to cause cancer especially in the bladder when introduced into the living body. For this reason, it has been strongly desired to provide dyes which are free of any hazard of causing cancer and serviceable as substitutes for polyazo dyes of the benzidine type and which are equivalent or superior to the conventional polyazo dyes with respect to dyeablility and abovementioned characteristics.

A main object of this invention is to provide novel and useful dyes which fulfil the above requirements and processes for preparing the same.

Other objects and advantages of this invention will be apparent from the following description.

The present invention provides novel polyazo dyes represented by the formula of R R2 p- A-N=N -N=N Q v W (SO Z) (I) wherein A is an aromatic ring having or not having a substituent, B is an aromatic ring having at least one substituent selected from the group consisting of amino. substituted amino and hydroxyl groups; X is CH or N; Y is one species selected from the group consisting of NH, N-NH N-R O and S, R being a hydrogen atom, alkyl group, aryl group, amino group or w-hydroxyalkyl group; Z is a hydrogen atom, alkali metal, NH group or amine salt residue; n is l or 2; and each of R and R is a hydroxyl or amino group, R being an amino group when R is a hydroxyl group, or a hydroxyl group when R is an amino group.

The present invention has been accomplished based on the novel finding that the new compounds of the formula (I) give very excellent colors and that they are almost as excellent as the conventional polyazo dyes of benzidine-type in dyeability, solubility in water and chemical stability but have no carcinogenic property and are very low in toxic properties.

Preferable examples of novel polyazo dyes represented by the foregoingiformula (I) are those wherein A is a phenyl group, naphthyl group or phenyl or naphthyl group having at least one substituent of a halogen atom, lower alkyl, lower alkoxy, amino, carboxy, nitro and sulfonic acid group; those wherein B is I o Me s lg llgjl or R being a hydrogen atom, alkyl group, aryl group,

amino group or w-hydroxyalkyl group. The most preferable examples of novel polyazo dyes represented by the foregoing formula (I) are those wherein A is Q @NO, @86 or those N'H NH 2 2 2 wherein B is brin NH @OH, 6

@ NHZ QNH @NH N3 SO H or SO H 5 CH NH ,1. I N those wherein is o SO H v or mula (I). These compounds are indicated by giving examples of A, R, R Z, n, X, Y and B in the formula K-N of i l R being the same as above. l N=N-B Listed in Table 1 below are typical examples of novel 35 polyazo dyes of this invention represented by the for- I 1 2 @lk I No. A R R Z in Y B Color N--N 2 purplish {M G @NH black N bluish n n 1| 1| 5 Q O p1 ack 4 D N-Q G t bluish 0 black Table 1-C0ntinued Color greenish black green green bluish black (iJH CH OH N 0 N NH black h h S h s k 1 n s n 1 c d e i e u a d e u e l l e r 1 r b b r 6 b 8 green Table l-'-C0ntinued l @K No. A R R 'n Y B Color l NN 25 H0 80 n u Q uG NH H H2N 26 H a 2 o 2 black 27 O N II I! II II II II greenish 2 black 28 HO s M bluish 5 o blck if? H II II II H I 50 1| 1| n n n HQN v greenish black 2 N-N 5 n n 11 n n n I CH OH NH N 2 z greenish Q .7 2 a N 64111 black E1H CH OH a 4 n n n II II purplish H CH OH H N I n I!" NH Sh E F 2 green v N'' H N 2 J 1 g n n I reddlsh 55 O N-O- b bl adk The novel polyazo dyes of this invention represented by the formula (I) do not containbenzidine'or its deriv atives as the basic componentand therefore .have no carcinogenic property and are extremely. low in their toxicity. v 1

The fact that the starting aromatic diamines, having the formula of (X and Y are the same as defined before) exhibit no carcinogenic property can be. seen from the following test.

CARCINOGENIC PROPERTY 4,4-diaminodiphenyltriazole was orally, administered to female rats of 40 days of age once every 3- days. After 9 months continuous administration, the animals were killed. The internal organs thereof were weighed and made into specimens of tissues to determin carcinogenic property. The results showed that no carci-; noma was observed at a dose of times as much as the, amount of benzidine at which the latter gave 50% carcinoma. r

The novel polyazo dyes are as excellent as ..the conventional dyes basically prepared from benzidine or its. derivatives with respect to -dyeability and-chemical stability and are almost equivalent to the known dyes in giving excellent colors. The present noveLdyes are readily soluble in water and effectively dye fibrous materials of hydroxyland/or amide-containing fibers. The dyeings obtained not only exhibit excellent colors equivalent to those given by the conventional polyazo dyes of benzidine type but also have good fastness to light, washing, acid and alkali.

The novel polyazo dyes of this invention can be produced by various processes as exemplified below.

PROCESS l A process comprising the steps of coupling, in a desired sequence, a tetrazotized product of aromatic diamine represented by the formula Q Q -N Q wherein X and Y are the same as'defined beforewith an aminonaphtholsulfonic acid represented by the formula v (III) aromatic amine represented by the formula l, A un, v

wherein is the same as defined before.

PROCESS 2 A process comprising the steps of coupling a tetrazotized product of aromatic diamine of the formula (II) with an aminonaphtholsulfonic acid of the formula (III), coupling theresulting product with a diazotized product of aromatic amine of the formula (V), and coupling the product obtained with an aromatic compound of the formula (IV).

PROCESS 3 A process comprising the steps of coupling an aminonaphtholsulfonic acid of the formula (III) with a diazotized product of aromatic amine of the formula (V) to prepare a compound of the formula wherein A, R, R Z and n are, the same as defined before, coupling the compound with a tetrazotized product oraromatic diamine of the formula (II), and couplingthe resulting productwith an aromatic compound of the formula (IV). I

The novel dye of this invention can be prepared by any of the processes described above. However, if R of the compound represented by the formula (III) is OH (i.e.

. OH V i (s0 z) the processes 1 and 2 are preferable, whereas if R is NH (i.e.

NH OH the process 3 is desirable.

Examples of the aromatic diamine of the formula (wherein X and Y are the same as defined before) to be used as a material in this invention are 3,5-bis(p-aminophenyl)-l ,2,4-triazole, 3,5-bis(m-aminophenyl)-l ,2,4-

triazole, 2,5-bis(p-aminophenyl)-l ,3,4-oxadiazole, 2,5- b1s(m-aminophenyl)-l,3,4-oxadiazole, 2,5-bis(paminophenyl)- 1 ,3,4-thiadiazole, 2,5-bis(m-aminophenyl)-l ,3,4-thiadiazole, 2,5-bis(p-aminophenyl)- furan, 2,5-bis(m-aminophenyl)-furan, 2,5-bis(p-aminophenyU-pyrole, 2,5-bis(m-aminophenyl)-pyrole, 2,5- b1s(p-aminodiphenyl )-oxazole, 2,5-bis(m-aminodiphenyl)-oxazole, 2,5-bis(p-aminodiphenyl)-thiazole, 2,5-bis(m-aminodiphenyl)-thiazole, 2,5-bis(p-aminophenyl)-imidazole, 2,5-bis(m-aminophenyl)-imidazole, 2,5-bis(p-aminophenyl)-thiophene, 2,5-bis(m-aminophenyl)-thiophene, etc.

Examples of the aromatic amine of the formula (III) A-NH2 (lll) (wherein A is the same as defined before) to be used in this invention are aniline, methylaniline, ethylaniline, t-butylaniline, cyclohexylaniline, dimethylaniline, methoxyaniline, ethoxyaniline, nitroaniline, dinitroaniline, nitrochloroaniline, 2-aminodiphpenylether, 4-aminodiphenylether, 2-amino-2'-methyldiphenylether, 4- amino-4'-methyldiphenylether, 2-amino-2'-chlorodiphenylether, 4-amino-4-chlorodiphenylether, acetylaminoaniline, propionylaminoaniline, oxalylaminoaniline, aminophenylurea, benzoylaminoaniline, 3-chloro-benzoyl-aminoaniline, 4'-chlorobenzoylaminoaniline, 3'-methylbenzoylaminoaniline, 4- methyl-benzoylaminoaniline, 3 -nitrobenzoylaminoaniline, 4'-nitrobenzoylaminoaniline, 4-benzoylethylaminoaniline, 2-methyl-4-acetylaminoaniline, 2- methyl-S-acetyl-aminoaniline, 2-methyl-4-benzoylaminoaniline, 2-methyI-S-benzoylaminoaniline, 2-methyl-4-formylaminoaniline, 4-methyl-3-formylaminoaniline, 2-methyl-5-oxalyl-aminoaniline, 4- methyl-3-oxalylaminoaniline, chloroaniline, methylchloroaniline, methylmethoxyaniline, methoxychloroaniline, dimethoxyaniline, methoxyacetylaniline, methoxyacetylaminoaniline, methoxyoxalylaminoani line, 4-methylaniline-Z-sulfonic acid, 4-methoxyaniline-2-sulfonic acid, 4-ethoxyaniline-Z-sulfonic acid, 4-methylaniline-3-sulfonic acid, 4-methoxyaniline-3- sulfonic acid, aniline-Z-sulfonic acid, 5- acetylaminoaniline-2-sulfonic acid, 4-chloroaniline-3- sulfonic acid, 4-acetylaminoaniline-Z-sulfonic acid, 4-benzoylaminoaniline-Z-sulfonic acid, 4- oxalylaminoaniline-3-sulfonic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid, aminobenzoic acid, anicidine, naphthionic acid, etc. Among these especially preferable are aniline, 4-nitroaniline, aniline- 4-sulfonic acid and naphthionic acid.

The cpimpound represented by the formula wherein B is the same as defined before, usable as a material in this invention, includes aromatic amines, phenols or naphthols having or not having a substituent. Examples thereof are toluylenediamine, N,N- diethyl-N-acetyl-m-phenylenediamine, aminonaphthalene, aminonaphthalene sulfonic acid, aminonaphthalene disulfonic acid, aminonaphthol sulfonic acid, aminonaphthol disulfonic acid, acetylaminonaphthol sulfonic acid, acetylaminonaphthol disulfonic acid, benzoylaminonaphthol sulfonic acid, benzoylaminonaphthol disulfonic acid, l-chloro-8-naphthol-3,6-disulfonic acid, 3-aminophenol, N,N-(otoluyl)-m-aminophenol, 3-acetylaminophenol, 3- hydroxy-4-methyldiphenylamine, aniline, 3-aminotoluene, 1,3-phenylenediamine, 3-B-hydroxyethylaminoaniline, Z-methyl-l,3-phenylenediamine, 4- methyl-l,3-phenylenediamine, 3-acetylaminoaniline, 3-aminophenyl urea, 3-aminophenylglycine, 6-methyl- 3-aminophenylglycine, 1,3-phenylenediamine-4-sulfonic acid, 4-chloro-l,3-phenylenediamine, 4-nitro- 1,3-phenylenediamine, 3-aminoanisole, 3-dimethylaminoaniline, 3-oxalylaminoaniline, 3- glyconylaminoaniline, 2,4-diaminoacetoanilide, naphthol, naphtholsulfonic acid, naphthol-tri-sulfonic acid, phenol, cresol, chlorophenol, etc.

According to thisinvention the tetrazotization and diazotization in any of the foregoing processes can be effectively carried out exactly in conventional manners. For example, the starting aromatic diamine having the formula of co fee (X and Y are the same as defined before) is reacted with a nitrite in the presence of a mineral acid such as sulfuric acid, hydrochloric acid, etc., at a low temperature, preferably at 0 to 10C, to produce a tetrazotized product of the aromatic diamine. The diazotization of the aromatic amine having the formula of ANH (A is the same as defined before) can also be conducted under the same conditions as above.

Likewise, coupling can be effected in conventional manners. For example, the coupling is carried out at a temperature of lower than 25C, preferably 0 to 5C for 10 minutes to 24 hours. The pH of the reaction system may vary over a wide range and may be suitably selected in accordance with the kind of the reactants to be coupled. The sequence of reaction and pH of the reaction system in the above processes are illustrated as follows, in which AA: shows aromatic amine of the formula (V),

l-ANS: shows l-amino-8-naphtolsulfonic acid of the formula (Z and n are the same as defined before), 8-ANS: shows S-amino-l-naphtholsulfonic acid of the formula NH OH (Z and n are the same as defined before),

ADA: shows aromatic diamine of the formula (II),

and

AC: shows an aromatic compound of the formula Process 2 AA 2 NS 1 i 3 alkaline LA acidic acidic or or neutral alkaline 2 n 1 3 1 AA acidic or alkaline alkaline neutral Process 3 1 2 3 I AA alkaline I'ANS acidic ADA acidic or alkaline M 1 n 2 I 3 m acidic or alkaline alkaline neutral or acidic The novel polyazo dyes of this invention are used for dyeing fibrous materials made of fibers having hydroxyl and/or amide groups. Exemplary of the fibers containing hydroxyl groups are cotton, hemp, cellulose, viscose rayon, cuprammonium artificial silk, vinylon (polyvinyl alcohol fiber), etc. Further examples of fibers having amide groups are silk, wool, polyamide synthetic fiber (nylon), polyurethane synthetic fiber, etc. The fibrous materials of these fibers include various products using these fibers such as thread, woven fabrics, knitted fabrics, felts, nonwoven fabrics, paper, leathers, etc.

The fibrous materials made of fibers containing hydroxyl groups and/or amide groups can be dyed or printed with the novelpolyaz o dyes of this invention in the same manner as conventionally practiced with this type of polyazo dyes. For instance, to dye a fibrous material of cotton, it is suitable to employ a dyeing bath having a pH of 8 to 10 and containing 1 to 8% by weight of a dye and 5 to 40% by weight of an inorganic salt, based on the fibrous material to be dyed. The fibrous material is placed in the bath with a liquor ratio of l 20 to 1 40. The bath is then gradually heated and maintained at a temperature approximate to the boiling point for 20 to 50 minutes for dyeing- When dyed, the fibrous material is taken out, roughly washed with water, squeezed and dried. Further fibrous materials of fibers having amide groups can be dyed within a wide pH range of from acidic to alkaline but, in general, they are preferably dyed in neutral to acidic pH range, most preferably at a pH of about 2 to 7. In the case where a fibrous material of wool is to be dyed, for example, it is preferable to use a dyeing bath having a pH of 2 to 7 and containing 3 to 10% by weight ofa dye and 1 to 5% by weight of concentrated sulfuric acid or acetic acid, based on the fibrous material to be dyed. The fibrous material is placed in the bath zit-60C with a liquor ratio of l 30 to 1 40. The bath is then heated gradually to the boiling point and maintained at this temperature for 30 to 90 minutes for dyeing. When dyed, the firbous material is taken out, roughly washed with water, squeezed and dried. In the case where a firbous mate rial of silk is to be dyed, for example, it is preferable to employ a dyeing bath having a pH of 7 to 10 and containing 50 to 300% by weight of a dye and 0.5 to

by weight of an inorganic salt, based on the weight of the fibrous material to be dyed. The firbous material is placed in the bath with a liquor ratio of l 50 to 1 150 and heated at to 100C for 15 to minutes. When dyed, the fibrous material is taken out and treated in the same manner as above.

Tothe dyeing bath can be added various additives conventional in the art, such as, accelerating agents, level dyeing agents, retarding agents, etc. Examples of accelerating agents are sodium chloride, sodium sulfate, various surfactants, etc. Level dyeing agents and retarding agents are, for example, higher alcohol detergents, Turkey red oil, Marseille soap, Monopole soap, silk scouring waste, sodium carbonate, sodium pyro phosphate, etc. Further, the fibrous material dyed with the present dye can be subjected to conventional aftertreatment. For such purpose there can be used acetic acid, formaline, polyethylene polyamines, cation surfactants, developers, metal salts, etc.

EXAMPLE 1 25 g (0.1 mol) of 3,5-bis(p-aminophenyl)-l,2,4- triazole (aromatic diamine) was dissolved in 60 g of concentrated hydrochloric acid and 60 g of water with heating and the resulting solution was placed into a mixture of g of water and 100 g of ice'. Next, to the above solution was added at 0C a'solution' of 14 g'(0.2

mol) of sodium nitrite in 50 g of water to tetrazotize the solution. An aqueous solution of 36.4 g (Olmol) of sodium 1-amino-8-naphthol-3,o di-sulfonate was added to the tetrazotized solution, and the mixture wa stirred at 0C for 3 to 6 hours.

An aqueous solution of sodium carbonate was then added to the resulting solution to make it alkaline. To this solution was then added a diazotized solution previously prepared by dissolving 10 g (about 0.1 mol) of aniline (aromatic amine) in 30 g of concentrated hydrochloric acid and 100 g of water and further adding 7g (0.1 mol) of sodium nitrite at 0C. The mixture was stirred at 0C for 2 hours.

Subsequently, hydrochloric acid was added to the solution obtained to make it acidic. A solution of '12 g (0.12 mol) of m-phenylenediamine (aromatic compound) in 200 g of water was then added to the solution, and the mixture was stirred overnight to complete the reaction. The product obtained was filtered with suction, washed with water and then with ethyl alcohol and dried to obtain a dye, which had a structure of Dye No. 36 and was bluish black.

EXAMPLES 2 TO 16 The components listed in Table 2 below are used as aromatic diamines (H NX-NH aromatic amine and aromatic compound according to Example 1 to obtain various dyes in the same manner as in Example 1. The dyes and their colors obtained are listed in Table 2 below.

Table 2 Example Aromatic Aromatic diamine Aromatic compound Produced Color No amine dye (Dye No.)

2 p-nitroaniline 3,5-bis(p-aminophenyl)- m-phenylenedi- 35 reddish l ,2.4-triuzole amine black 3 aniline 3,5-bis(p aminophenyl m toluylene- 34 blusih l-ethoxy-1,2,4-tia2ol diamine black 4 aniline 3,5-bis(m-aminophenyl p-phenol 22 reddish 1,2,4-triazole black Table 2-continued Example Aromatic Aromatic diamine Aromatic compound Produced Color No. amine dye (Dye No.)

5 p-nitroaniline 3 ,5-bis( m-aminophenyl 44 greenish 1,3,4-oxadiazole diamine black 6 aniline 2 5-bis(p-aminophenyl) m-toluylene- 38 greenish 1,3 ,4-oxadiazole diamine black 7 p'nitroaniline 2,5'bis(m aminophenyl m-toluylene- 40 greenish 1,3A-oxadiazole diamine black 8 aniline 2,5'bis(p-aminophenyl)- m-phenylene- 26 purplish furan diamine black 9 aniline 2,5-bis(p-aminophenyl) mphenylenel purplish 1,3,4-thiadiazole diamine black 10 aniline 2,5-bis( p-aminophenyl m-toluylene- 3 bluish oxazole diamine black I l p-nitroaniline 2,5-bis(m-aminophenyl)- m-toluylene- 4 bluish oxazole diamine black 12 aniline 2.5-bis(p-aminophenyl)- imidazole phenol 5 green l3 sulfanilic 3.5-bis(p-aminophenyl m-phenylene- 41 bluish acid oxazole diamine black l4 aniline 3,S-bis(p-aminophenyl)- m-phenylene- 33 purplish 4-phenyl-triazole diamine black 15 p-nitroaniline 3 ,5 bis( p-aminophenyl m-phenylene- 27 bluish furan diamine black 16 salfanilic 2.5-bis( p-aminophenyl m-naphthylamine 6 bluish acid imidazole black EXAMPLE 17 where M is NH or OH; M' and M are the same or 13.0 g of a hydrochloric acid salt of aniline was dissolved in a mixture of 23 g of hydrochloric acid and 50 g of H 0, and the resulting solution was diazotized with 69 g of sodium nitrite at 0C. A neutral aqueous solution of 31.9 g of 1-amino-8-naphthol-3,6-disulfonic acid was then added to the diazotized product. The mixture was stirred overnight to effect complete coupling. N21 CO was dissolved in the resulting product to adjust the same to a pH of7. Subsequently, in a mixture of 100 g of water and 56 g of 30% HCl, 25.2 g of 2,5- bis(p-aminophenyl)-l ,3,4-oxadiazole was tetrazotized at 0C with 13.8 g of sodium nitrite. The first coupled product was treated with 20 g of Na CO and was thereafter added to the tetrazotized product of 2,5-

bis(p-aminophenyl)-l ,3,4-oxadiazole which had previously been neutralized with an aqueous solution of sodium acetate. The mixture was stirred to complete coupling. To the resulting product was added a solution prepared from 100 g of H 0, 17 g of Na CO and 9.4 g

of phenol, and the mixture was stirred for 12 hours. The dye obtained was then subjected to salting out with common salt, followed by filtration and drying. The dye had the structure of Dye No. 39 and dyed silk in green.

What we claim is: 1. A polyazo dye represented by the formula:

wherein A is phenyl, naphthyl or phenyl or naphthyl substituted with chlorine, lower alkyl, lower alkoxy, amino, carboxy, nitro, SO H or SO Na; B is different and are H, N0 lower alkyl, SO H, SO Na or N(R) the members R being independently H, N0 lower alkyl or phenyl substituted with lower alkyl; X is CH or N; Y is NH, N-NH N-R, O or S, where R is lower alkyl; Z is hydrogen, alkali metal, or NH n is l or 2; and each of R and R is hydroxyl or amino, R being amino when R is hydroxyl or R is hydroxyl when R is amino.

2. The dye of claim 1 wherein said in the formula is meow 3 The dye of claim 1 wherein The dye of claim 1 wherein said 3,928,310 V 21 22 U- iS I is n The dye of clam 1 wherein Sam 10. The dye of claim 1 wherein said ig jis l Q The dye of claim 1 wherein said 11. The dye of claim 1 wherein said g :5- is is 7. The dye of claim 1 wherein said 12. The dye of claim 1 wherein said A is is Q or The dye of claim 1 wherein said 13. The dye of claim 1 wherein said B is selected 9. The dye of claim 1 wherein said from the group consisting of CH S0 H and SOH 

1. A POLYAZO DYE REPRESENTED BY THE FORMULA:
 2. The dye of claim 1 wherein said
 3. The dye of claim 1 wherein
 4. The dye of claim 1 wherein said
 5. The dye of claim 1 wherein said
 6. The dye of claim 1 wherein said
 7. The dye of claim 1 wherein said
 8. The dye of claim 1 wherein said
 9. The dye of claim 1 wherein said
 10. The dye of claim 1 wherein said
 11. The dye of claim 1 wherein said
 12. The dye of claim 1 wherein said A is
 13. The dye of claim 1 wherein said B is selected from the group consisting of 